JP2001192526A - Curable coating resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable coating resin composition which is excellent in flexural resistance, scratch resistance, and adhesion to a molded polyolefin resin. SOLUTION: This resin composition is prepared by compounding a curing agent comprising an isocyanate compound or an alkyl-etherified amino resin into a resin, as the main ingredient, which is an esterification product of a carboxyl-containing chlorinated polyolefin and a polyol resin and/or a mixture of the esterification product and a polyol resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating resin composition used for the purpose of protection or cosmetics of polyolefin-based resins, for example, polypropylene, polyethylene, ethylene-propylene copolymer, styrene-butadiene copolymer and the like. The present invention relates to a composition which is used as a binder resin for a primer, a paint, an ink or an adhesive which has excellent adhesiveness to sheets, films and molded articles of the above and other excellent physical properties.

[0002]

2. Description of the Related Art Plastics are widely used as materials for automobile parts, electric parts, building materials, etc. in recent years because of their high productivity, wide design freedom, and many advantages such as light weight, rust prevention and impact resistance. Used. In particular, polyolefin-based resins are inexpensive and have many excellent properties such as moldability, chemical resistance, heat resistance, water resistance, and good electrical properties.
It is widely used as an industrial material, and it is one of the materials whose demand is expected to grow in the future. However, polyolefin resins are polyurethane resins,
Unlike synthetic resins having polarity, such as polyamide resins, acrylic resins, and polyester resins, they have the disadvantage that they are difficult to paint and adhere because they are non-polar and crystalline.

[0003] Conventionally, the surface of a polyolefin-based resin molded article is activated by plasma treatment or gas flame treatment to improve the adhesion. However, this method is complicated and requires a large amount of equipment and time. It has drawbacks such as a large loss, and the surface treatment effect varies due to the complexity of the shape of the molded product and the effects of pigments and additives in the resin.

As a method of coating without such a pretreatment, various primer compositions such as those found in automotive bumper coating have been proposed, especially chlorinated polyolefins having strong adhesion to polyolefin resins. Is often used. However, chlorinated polyolefins are inferior in resistance to ultraviolet light and heat, and cannot be said to have sufficient coating film performance, and improvement of these has been strongly desired. As a means for improving these properties, attempts have been made to use a mixture of an acrylic resin or an alkyd resin having good paint properties. However, acrylic resins and alkyd resins inherently have poor compatibility with chlorinated polyolefins, and thus cause problems such as poor dispersion of pigments and a decrease in gloss of a coating film, and significantly impairing the appearance.

For example, JP-A-54-127436 discloses 2,2
A resin composition for coating obtained by mixing an alkyd resin containing 2,4-trimethylpentane-1,3-diol as a polyol component and a chlorinated polyolefin, and JP-A-61-2
No. 8561, acrylic-modified chlorinated polypropylene, and a graft polymer of polyester and alkyd resin,
There has been proposed a resin composition for coatings containing a graft polymer of polyester and polyisocyanate as a main component.
However, chlorinated polyolefins are inherently poorly compatible with the various polyol resins described above, so that even when mixed with these, opacity or two-layer separation occurs, and a uniform and transparent solution cannot be obtained. It cannot be a binder resin such as a primer or an adhesive.

JP-A-7-10940 proposes a binder resin composition obtained by reacting a polyester polyol and a radically polymerizable unsaturated compound with a carboxyl group-containing chlorinated polyolefin. Since there is a possibility that gelation or a decrease in compatibility may occur due to a cross-linking reaction accompanying the grafting of the polymerizable unsaturated substance, this also cannot be a good binder resin for paints, primers, adhesives and the like.

The present inventors have prepared a coating resin composition for a polyolefin-based resin having excellent compatibility with an acrylic resin or an alkyd resin and having sufficient adhesion to a polyolefin substrate, as disclosed in Japanese Patent Application No. 11-237417. No. has already proposed. That is, it is a composition comprising an esterification reaction product of a carboxyl group-containing chlorinated polyolefin and a polyol resin and / or a mixture of the esterification reaction product and a polyol resin. However, even with this composition, the strength of the coating film was insufficient, such as cracking when the coating film was bent or scratching when scratched with a nail due to insufficient cohesive strength of the coating film.

[0008]

SUMMARY OF THE INVENTION The present invention relates to Japanese Patent Application No.
A coating, primer, and printing ink that solves the above-mentioned problems by improving the shortage of the coating film, which is a drawback of the composition proposed in 37417, and is far superior to conventional chlorinated polyolefin modified products. It is an object of the present invention to provide a curable coating resin composition such as an adhesive.

[0009]

Means for Solving the Problems The present inventors have conducted various experiments to solve the above-mentioned problems, and as a result, they have been selected from α, β-unsaturated carboxylic acids and / or acid anhydrides thereof. It consists of an esterification reaction product of a carboxyl group-containing chlorinated polyolefin obtained by graft modification using one or more compounds and a polyol resin and / or a mixture of the esterification reaction product and a polyol resin. Resin as a main component, a curable coating resin composition obtained by blending an isocyanate compound or an alkyl etherified amino resin as a curing agent with this, bending resistance, scratch resistance,
Furthermore, they have found that they have excellent adhesion to a polyolefin substrate, and have reached the present invention.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The carboxyl group-containing chlorinated polyolefin used in the present invention is obtained by melting a polyolefin and, if necessary, converting a polyolefin molten resin degraded by thermal decomposition into a batch type or a continuous type. In the presence of an agent, the unsaturated carboxylic acid monomer is graft-copolymerized, then dispersed or dissolved in water or a solvent such as carbon tetrachloride or chloroform, and pressurized in the presence of a radical generator or under irradiation with ultraviolet light. Or 50 under normal pressure
After blowing chlorine gas in a temperature range of up to 120 ° C. to perform a chlorination reaction, the solvent can be distilled off, and a solution can be obtained in which a stabilizer is added and the solution is replaced with an organic solvent such as toluene or xylene. After chlorination, the chlorinated solvent is concentrated under reduced pressure, a stabilizer is added, and then the solvent is completely removed by a vented extruder or the like equipped with a vent port for distilling off the solvent under reduced pressure. You can also get.

As a radical generator, for example, di-tert-
Butyl peroxide, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide,
There are peroxides such as tert-butyl peroxide benzoate, methyl ethyl ketone peroxide, di-tert-butyl diperphthalate, and azonitriles such as azobisisobutyronitrile. Examples of the unsaturated carboxylic acid monomer and its anhydride used in the graft copolymerization reaction include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, fumaric acid, mesaconic acid, and itaconic acid. , Itaconic anhydride, aconitic acid, aconitic anhydride and the like.

As the stabilizer for the chlorinated polyolefin, the stabilizer used for polyvinyl chloride, which is a chlorine-based resin, can be applied as it is. For example, calcium stearate, metal soaps such as lead stearate, lead oxide, inorganic acid salts such as tribasic lead sulfate, organic metal compounds such as dibutyltin dilaurate, dibutyltin malate, hydrotalcite compounds, epoxy compounds Kind. However, among these, epoxy compounds are most commonly used. For example, epoxidized soybean oil or epoxidized linseed oil obtained by epoxidizing a vegetable oil having a natural unsaturated group with a peracid such as peracetic acid. Epoxidized fatty acid esters obtained by epoxidizing unsaturated fatty acid esters such as oleic acid, tall oil fatty acid and soybean oil fatty acid. Epoxidized alicyclic compounds represented by epoxidized tetrahydrophthalate. Bisphenol A or polyhydric alcohol and epichlorohydrin condensed, for example, bisphenol A glycidyl ether,
Ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and the like. Also, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, sec-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, phenol polyethylene oxide glycidyl ether, etc. Monoepoxy compounds.

The carboxyl group-containing chlorinated polyolefin used in the present invention is prepared by preparing a solution of the chlorinated polyolefin obtained by chlorinating the polyolefin by the above-mentioned method, and then adding the unsaturated carboxylic acid monomer and its anhydride in the presence of a radical generator. It can also be obtained by graft copolymerizing the product. As the radical generator, unsaturated carboxylic acid monomer and anhydride thereof used in the graft copolymerization reaction, those described above can be used as they are.

As the raw material polyolefin for the carboxyl group-containing chlorinated polyolefin used in the present invention, crystalline polypropylene, a propylene-α-olefin copolymer or a propylene-butene-ethylene copolymer which is a terpolymer is preferable. . Crystalline polypropylene means isotactic polypropylene and syndiotactic polypropylene. Weight average molecular weight 10,000 ~
300,000 can be used.

On the other hand, the propylene-α-olefin copolymer is obtained by copolymerizing α-olefin with propylene as a main component, and either a block copolymer or a random copolymer can be used. Examples of the α-olefin component include ethylene, 1-butene, 1-pentene, 1-
Hexene, 1-heptene, 1-octene, 4-methyl-1-pentene and the like can be exemplified. The content of the propylene component is optimally 50 to 98 mol%, and if it is less than 50 mol%, the adhesion to polypropylene is reduced. On the other hand, if it exceeds 98 mol%, the flexibility of the coating film becomes poor.

The polyol resin used in the present invention is a polyhydric alcohol having two or more hydroxyl groups in the molecule, such as acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, cellulose acetate butyrate, nitrified cotton, and alkyd resin. Or a modified product thereof.

Acrylic polyl is an acrylic resin obtained by copolymerizing a monomer having a hydroxyl group such as a hydroxyl ester of (meth) acrylic acid and (meth) acrylic acid ester monomers. The polyester polyol is a polyester resin obtained by subjecting a dibasic acid and an excess polyhydric alcohol to an esterification reaction.

The polyether polyol is a resin containing, as a main component, polypropylene glycol obtained by addition-polymerizing propylene oxide or ethylene oxide to a polyhydric alcohol.

The epoxy polyol is a solid epoxy resin having a hydroxyl group or an amine-modified resin of a bisphenol A type epoxy resin.

Further, cellulose acetate butyrate is
It is a cellulose derivative obtained by further butyrylating a partially acetylated product of cellulose.

Further, nitrified cotton is a cellulose derivative obtained by treating a cellulose raw material such as paper or cotton with a mixed solution of sulfuric acid and nitric acid.

The alkyd resin is a type of polyester resin obtained by a polycondensation reaction between a polyhydric alcohol and a polybasic acid. Glycerin as a polyhydric alcohol component,
Examples of polybasic acid components such as pentaerythritol and ethylene glycol include phthalic anhydride, maleic anhydride, and rosin / maleic anhydride adduct.

The chlorine content of the carboxyl group-containing chlorinated polyolefin is preferably from 10 to 50% by weight. Chlorine content 5
If it exceeds 0% by weight, the adhesion to the polyolefin will be poor, and if the chlorine content is less than 10% by weight, the solution state will be poor.

The graft ratio of the unsaturated carboxylic acid monomer and its anhydride in the carboxyl group-containing chlorinated polyolefin is preferably 1 to 10% by weight. If the graft ratio exceeds 10% by weight, gelation occurs during an esterification reaction with a polyol resin having a hydroxyl group or the like, and adhesion to a polyolefin becomes poor. When the graft ratio is less than 1% by weight, adhesion to the overcoat is deteriorated, and the amount of generated ester is limited, so that the contribution to compatibility and pigment dispersibility is reduced.

The carboxyl group-containing chlorinated polyolefin is esterified with the polyol resin by appropriately diluting the carboxyl group-containing chlorinated polyolefin with a solvent, premixing the polyol resin, adding a catalyst, and then heating. It is basically to react. The solvent used in the reaction is preferably an aromatic solvent such as toluene and xylene, and an ester solvent such as ethyl acetate and butyl acetate; a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone; ethanol, isopropanol;
Alcohol solvents such as n-butanol, aliphatic solvents, cycloaliphatic solvents and the like may be used in combination.

Examples of the catalyst used in the esterification reaction include acidic catalysts such as sulfuric acid, p-toluenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, and sulfate.
Organic tin compounds such as butyltin malate, other antimony trioxide, alumina and the like.

The weight ratio of the carboxyl group-containing chlorinated polyolefin and the polyol resin to be esterified in the present invention is preferably in the range of 99/1 to 50/50.
If the ratio of the carboxyl group-containing chlorinated polyolefin exceeds 99 parts by weight, the chlorinated polyolefin component increases when used as a resin for one-coat paints, which causes problems such as poor weather resistance and yellowing and gloss reduction. On the other hand, if the ratio of the carboxyl group-containing chlorinated polyolefin is less than 50 parts by weight, the chlorinated polyolefin component as an adhering component is insufficient, and the adhesion to the polyolefin substrate is poor.

[0028] The esterified product alone shows well-balanced coating film properties, but further includes various polyol resins,
For example, acrylic polyol, polyester polyol,
Even more coating film properties are expected by mixing other resins such as polyether polyol, epoxy polyol, cellulose acetate butyrate, nitrified cotton, alkyd resin or its modified products in a weight ratio of 90/10 to 10/90. it can. When the proportion of the esterified product exceeds 90 parts by weight, the chlorinated polyolefin component increases when used as a resin for one-coat paints, which causes problems such as poor weather resistance, yellowing and a decrease in gloss. On the other hand, if the ratio of the esterified product is less than 10 parts by weight, the chlorinated polyolefin component as an adhering component is insufficient, and the adhesion to the polyolefin substrate is poor.

The resin obtained by the esterification reaction of the present invention and / or the resin comprising a mixture of the esterification reaction product and a polyol resin may be cured by blending an isocyanate compound or an alkyl etherified amino resin as a curing agent. Thereby, the physical properties required for paints and adhesives, such as bending resistance and scratch resistance, can be improved.

The isocyanate compound used in the present invention includes aromatic, aliphatic and alicyclic organic diisocyanates, such as tolylene diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and 1,4-tetramethylene diisocyanate. 1,1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate,
4-cyclohexyl diisocyanate and the like. In addition, these organic diisocyanates may be used after being modified into isocyanate derivatives such as buret, isocyanurate, and trimethylolpropane adduct.

Further, a blocked isocyanate compound obtained by blocking the isocyanate with a blocking agent can also be used. Examples of the blocking agent include oximes such as methyl ethyl ketoxime, cyclohexanone oxime, formaldoxime and acetoaldoxime, phenols such as phenol and cresol, alcohols such as methanol, benzyl alcohol and ethylene glycol monomethyl ether, and methyl acetoacetate. Active methylenes such as dimethyl malonate, amides such as acetanilide and acetic acid amide, imides, amines, imidazoles, ureas, carbamates, imines, mercaptans, sulfites, lactams, etc. is there.

Compounds having two or more isocyanate groups per molecule, such as urethane resins having free isocyanate groups obtained by reacting the above-mentioned organic diisocyanates with high molecular polyols such as polyether polyols and polyester polyols Can be used.

Reactivity and Deblocking Reactivity of Esterification Reaction Product of Carboxyl Group-Containing Chlorinated Polyolefin with Polyol Resin and / or Resin Consisting of Mixture of Esterification Reaction Product and Polyol Resin with Isocyanate Compound as Curing Agent A reaction catalyst can be used for the purpose of promoting the reaction. Examples of the reaction catalyst include dibutyltin dilaurate, dibutyltin fatty acid salt, dibutyltin diacetate, tetra-n-butyl-1,3-diacetoxy-distannoxane,
Examples thereof include dilauryloxy-distannoxane, di-n-butyltin oxide, mono-n-butyltin oxide, stannous octylate, and zinc octenoate.

The alkyl etherified amino resin used as the curing agent of the present invention is obtained by reacting an amino compound such as urea, melamine or benzoguanamine with formaldehyde to form a methylol and then etherifying it with a lower alcohol such as methanol or butanol. Obtained by
For example, n-butyl etherified urea resin, isobutyl etherified urea resin, methyl etherified melamine resin, n-butyl etherified benzoguanamine resin, and the like.

Further, in order to promote the reaction between an alkylated etherified amino resin and a resin comprising an esterification reaction product of a carboxyl group-containing chlorinated polyolefin and a polyol resin and / or a mixture of the esterification reaction product and a polyol resin. An acidic catalyst can be used. For example, there are alcohol solutions of hydrochloric acid, salts of strong acids such as ammonium chloride, phosphates such as monobutyl phosphate, and organic sulfonic acids such as p-toluenesulfonic acid.

The amount of the curing agent added to the esterification reaction product of the carboxyl group-containing chlorinated polyolefin and the polyol resin and / or the resin comprising the mixture of the esterification reaction product and the polyol resin is determined by the hydroxyl group content of the composition. Can be determined as appropriate. That is, the isocyanate group is used when the curing agent is an isocyanate compound, and the alkoxy group is used when the curing agent is an alkyl etherified amino resin in the range of 0.5 to 1.5 mol per mol of the hydroxyl group contained in the composition. If it is less than 0.5 mol, the effect of crosslinking is small,
If the amount exceeds 1.5 mol, unreacted curing agent remains, which is not preferable.

The curable coating resin composition of the present invention may be used after being coated as it is.
Solvents and other additives such as an ultraviolet absorber, an antioxidant, and a pigment settling inhibitor are added, kneaded and dispersed, and used as a paint or printing ink. Further, it can be used as an adhesive for various plastics such as polypropylene resin or a primer for coating.

[0038]

The main feature of the present invention is that a resin consisting of an esterification reaction product of a carboxyl group-containing chlorinated polyolefin and a polyol resin and / or a mixture of the esterification reaction product and a polyol resin is used as a main component. A curable coating that improves bending resistance and scratch resistance by blending an isocyanate compound or an alkyl etherified amino resin as a curing agent, and shows good adhesion to polyolefins that were difficult to adhere to before. It is to obtain a resin composition.

That is, when the hydroxyl group of the unreacted polyol resin which has not been esterified with the carboxyl group in the carboxyl group-containing chlorinated polyolefin or the hydroxyl group in the polyol resin further mixed is an isocyanate compound as the curing agent Reacts with an isocyanate group, or, when the curing agent is an alkyl etherified amino resin, with an alkoxy group to form a crosslinked structure, giving cohesion to the coating film,
It is considered that physical properties such as bending resistance and scratch resistance are improved.

[0040]

Next, the present invention will be described in more detail by way of examples.

(Production Example 1) The melt viscosity at 180 ° C. was 25.
6 kg of an ethylene-propylene copolymer having an ethylene content of 6 mol% at 00 mPas was placed in a three-necked flask equipped with a stirrer and a condenser for refluxing the monomer, and the oil kept constant at 180 ° C. It was completely melted in the bath. After the atmosphere in the flask was replaced with nitrogen, maleic anhydride was added while stirring.
240 g was charged over about 5 minutes, and then 24 g of di-tert-butyl peroxide was dissolved in 50 ml of heptane, and charged over about 30 minutes from a dropping funnel. At this time, the inside of the system was maintained at 180 ° C., and the reaction was further continued for about 1 hour. Then, unreacted maleic anhydride was removed over about 30 minutes while reducing the pressure inside the flask with an aspirator. Next, this product was charged into a glass-lined reaction vessel, and 100 liters of chloroform was added thereto, and then completely dissolved at 100 ° C. under a pressure of 2.5 kg / cm ² . Further, azobisisobutyronitrile was added in an amount of 0.1% by weight based on the resin content, and a chlorination reaction was carried out by blowing chlorine gas from the bottom of the reactor while maintaining the temperature at 90 ° C. After completion of the reaction, chloroform as a solvent was distilled off with an evaporator, and the solvent was replaced with a mixed solvent of toluene / cyclohexane = 65/35 (w / w). Epiol TB (epichlorohydrin derivative, manufactured by NOF Corporation) was used as a stabilizer. 4 for solids
The concentration was adjusted by adding wt% to obtain a toluene / cyclohexane mixed solution of a carboxyl group-containing chlorinated ethylene-propylene copolymer having a solid content of 20 wt%. At this time, the chlorine content was 18.0% by weight (based on solid content), and the graft ratio of maleic anhydride was 2.5% by weight (based on solid content).

(Production Example 2) Number average molecular weight is about 15,000
The same melting reaction as in Production Example 1 was performed except that 6 kg of isotactic polypropylene, 420 g of maleic anhydride, and 42 g of di-tert-butyl peroxide were used, and then a chlorination reaction was performed. The solvent chloroform was concentrated under reduced pressure by an evaporator, and a hydrotalcite compound was added as a stabilizer at 4% by weight based on the solid content.Then, a vented extruder equipped with a vent port for distilling off the reaction solvent under reduced pressure was used. Chloroform was completely removed, extruded into strands, cooled with water, and a solid of carboxyl group-containing chlorinated polypropylene pelletized with a water-cooled pelletizer (Model: KM-150, Katsu Seisakusho Co., Ltd.) was obtained. At this time, the chlorine content was 35.0% by weight (based on solids), and the graft ratio of maleic anhydride was 4.3% by weight (based on solids).

(Production Example 3) 6 kg of a propylene-butene-ethylene copolymer having a weight average molecular weight of 120,000, a propylene component of 75 mol% and an ethylene component of 8 mol% was charged into a glass-lined reactor, and 100 liters were added. After completely dissolving under the condition of ² kg / cm ² -110 ° C, chlorine gas is blown from the bottom of the reactor while irradiating with ultraviolet rays to obtain a reaction solution having a chlorine content of 12% by weight. Was. Next, after concentration by an evaporator, 4% by weight of Epiol TB as a stabilizer was added to the solid content, and then carbon tetrachloride as a reaction solvent was replaced with toluene, and chlorinated propylene having a solid content concentration of 30% by weight was used. -A toluene solution of a butene-ethylene copolymer was obtained. Next, 1,000 g of this chlorinated propylene-butene-ethylene copolymer toluene solution was placed in a three-necked flask equipped with a stirrer, a dropping funnel, and a condenser for refluxing the monomer, and the atmosphere in the flask was replaced with nitrogen. While stirring at 90 ° C., 3 g of benzoyl peroxide was added, and the mixture was further stirred for about 30 minutes. Next, 15 g of methacrylic acid was added from the dropping funnel over about 30 minutes, and after further reacting for 3 hours, the concentration was adjusted. I got The chlorine content at this time is 11.3% by weight
The graft ratio of methacrylic acid (on solids) was 4.7% by weight (on solids).

Table 1 summarizes the carboxyl group-containing chlorinated polyolefins obtained in Production Examples 1 to 3.

[0045]

[Table 1] Table 1 Contents of carboxyl group-containing chlorinated polyolefins of Production Examples 1-3

(Production Example 4) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example 1 and phthalkid V901
(Vinyl-modified alkyd resin, manufactured by Hitachi Chemical Co., Ltd., solid content: 50% by weight) 10.5 g was mixed in a three-necked flask equipped with a stirrer and a condenser, and di-n-octyltin dilaurate was added to the resin. After adding 0.1% by weight based on the solid content, the temperature was increased to 85%.
The reaction was carried out for 5 hours while maintaining the temperature at 0 ° C, and the concentration was adjusted with toluene to produce a coating resin composition (1) for a polyolefin-based resin having a solid content of 20% by weight.

(Production Example 5) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example 1 and cellulose acetate butyrate (acetyl group content: 14% by weight, butyryl group content: 37% by weight, solid content: 100) Weight%) 11.1 g was mixed in a three-necked flask equipped with a stirrer and a condenser, and 0.1% by weight of p-toluenesulfonic acid was added to the resin solids. The reaction was carried out for a period of time, and the concentration was adjusted with toluene to produce a coating resin composition (2) for a polyolefin resin having a solid content of 20% by weight.

(Production Example 6) 100 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example-2 and LR-193 (acryl polyol, manufactured by Mitsubishi Rayon Co., Ltd., solid content: 60% by weight) 29.
4 g, 400 g of toluene were mixed in a three-necked flask equipped with a stirrer and a condenser, and after adding di-n-butyltin dilaurate to the resin solids by 0.5% by weight, the temperature was maintained at 85 ° C. The reaction was carried out for 5 hours, and the concentration was adjusted with toluene to produce a coating resin composition (3) for a polyolefin resin having a solid content of 20% by weight.

(Production Example 7) 100 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example-2 and desmophen 690
(Polyester polyol, Sumitomo Bayer Urethane Co., Ltd.)
33.3 g, 400 g of toluene were mixed in a three-necked flask equipped with a stirrer and a condenser, and 0.5% by weight of antimony trioxide was added to the resin solids.
The reaction was carried out for 5 hours while maintaining the temperature at 85 ° C., and the concentration was adjusted with toluene to produce a coating resin composition (4) for a polyolefin resin having a solid content of 20% by weight.

(Production Example 8) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example 3 and desmophen 1900
81.8 g of U (polyether polyol, manufactured by Sumitomo Bayer Urethane Co., Ltd., solid content: 100% by weight) was mixed in a three-necked flask equipped with a stirrer and a condenser, and alumina was added to the resin solid content at 0.1%. After the addition of 5% by weight, the reaction was carried out for 5 hours while maintaining the temperature at 85 ° C, and the concentration was adjusted with toluene.
A coating resin composition (5) for a polyolefin resin having a solid content of 20% by weight was produced.

(Production Example 9) 500 g of the carboxyl group-containing chlorinated polyolefin obtained in Production Example 3 and Kuraray polyol
20 g of P-1010 (polyester polyol, manufactured by Kuraray Co., Ltd., solid content: 100% by weight) was mixed in a three-necked flask equipped with a stirrer and a condenser, and concentrated sulfuric acid was added to the resin solids at 0%. .
After adding 1% by weight, an esterification reaction was performed for 2 hours while maintaining the temperature at 110 ° C. Next, 8.4 g of t-butyl peroxyisopropyl carbonate was added, and a radically polymerizable unsaturated substance composed of 80 g of cyclohexyl acrylate and 20 g of 2-hydroxyethyl acrylate was added dropwise over 3 hours.The copolymerization reaction was further performed for 6 hours. The concentration was adjusted with toluene to produce a coating resin composition (6) for a polyolefin resin having a solid content of 20% by weight.

(Examples 1 and 2 and Comparative Examples 1 to 3) Primers were prepared according to the compositions shown in Table 2, and a performance test of the primers was performed. Table 3 shows the results.

[0053]

[Table 2] Table 2 Primer composition (weight ratio) Note) Sumidur N3500: Isocyanate curing agent (Sumitomo Bayer Urethane Co., Ltd., hexamethylene diisocyanate, isocyanurate)

1) Preparation of Primer After kneading for 1 hour with a sand mill except for the curing agent and the catalyst having the above primer composition, 12-13 seconds / 20 ° C. in a Ford cup # 4.
It was prepared by diluting with xylene to give a viscosity of. Those requiring a curing agent and a catalyst were added immediately before coating. 2) Coating method Primer is coated on a polyolefin substrate (ultra-high-rigidity polypropylene) washed with isopropyl alcohol to a thickness of 10 to 15
Paint using air spray to a thickness of 15 μm
After drying at room temperature for 2 minutes, a two-part curable urethane paint is spray-coated so that the film thickness becomes about 30 μm, dried at room temperature for 20 to 30 minutes, and then forcibly dried at 80 ° C. for 30 minutes, After being allowed to stand in the room for 3 days, it was subjected to a coating film test. 3) Evaluation method of coating film ・ Make 100 grids to reach the substrate at 2 mm intervals on the adhesive coated surface,
A cellophane adhesive tape was adhered thereon and peeled off in the 180 ° direction, and the number of remaining grids was checked.・ Leave the moisture-resistant painted plate in an atmosphere of 50 ° C and 98% relative humidity for 240 hours,
The state and adhesion of the coating film were examined. -The warm water- resistant coated plate was immersed in warm water of 40 ° C for 240 hours, and the state and adhesion of the coating film were examined. -Gasoline resistance The coated plate whose both ends were cut was immersed in regular gasoline, and it was judged by the time required to peel about 2 mm from the end of the cut coated surface.

[0055]

[Table 3] Table 3 Primer test results

(Examples 3 and 4 and Comparative Examples 4 to 6) Basecoat paints were prepared with the compositions shown in Table 4, and performance tests of the basecoat paints were performed. Table 5 shows the results.

[0057]

[Table 4] Table 4 Basecoat paint composition (weight ratio) Note) Melan 11: alkyl etherified amino resin hardener (butyl etherified urea resin, manufactured by Hitachi Chemical Co., Ltd., solid content: 60% by weight)

1) Preparation of Base Coat Paint After shaking for one hour with a shaker except for the curing agent and the catalyst of the above base coat paint composition, use a Ford cup # 4 for 12-13.
It was prepared by diluting with xylene to a viscosity of sec / 20 ° C. And for those that require a curing agent and a catalyst,
They were added just before painting. 2) Coating method The base coat paint is coated on a polyolefin substrate (ultra-high rigidity polypropylene) washed with isopropyl alcohol.
Paint using air spray to 30-35μm, 5
After drying at room temperature for ~ 10 minutes, a clear coat paint (two-part curable urethane) is spray-coated so that the film thickness is about 10 μm, dried at room temperature for 20-30 minutes, and then at 80 ° C for 30 minutes Was subjected to forced drying, left in a room for 3 days, and then subjected to a coating film test. 3) Evaluation method of coating film ・ Adhesion, moisture resistance, hot water resistance and gasoline resistance are the same as above.

[0059]

[Table 5] Table 5 Basecoat paint test results

(Examples 5, 6 and Comparative Examples 7 to 9) One-coat paints were prepared according to the compositions shown in Table 6, and performance tests of the one-coat paints were performed. Table 7 shows the results.

[0061]

[Table 6] Table 6 One-coat paint composition (weight ratio) Note) Desmodur Z4370: Isocyanate curing agent (Sumitomo Bayer Urethane Co., Ltd., isophorone diisocyanate, isocyanurate)

1) Preparation of one-coat paint A non-curing agent of the above one-coat paint composition was sand-milled.
After kneading for 1 hour, the mixture was diluted with xylene to a viscosity of 12 to 13 seconds / 20 ° C. using a Ford cup # 4. And
Those requiring a curing agent were added immediately before painting. 2) Coating method One-coat paint is applied to a polyolefin base material (styrene butadiene copolymer) washed with isopropyl alcohol using an air spray so as to have a film thickness of about 30 μm.
After drying at room temperature for 0 to 30 minutes, forcible drying was performed at 80 ° C. for 30 minutes. 3) Evaluation method of coating film- Adhesion, moisture resistance, hot water resistance Same as above. Gloss: Measured with a 60 ° specular gloss meter.・ Attach a cloth impregnated with butter on a butter resistant coated surface,
After standing for one day, the butter remaining on the coated surface was completely washed off, and the adhesion of the coating film was examined. -Alkali resistance The coated plate was immersed in a 0.1N alkaline aqueous solution for 120 hours, and the state of the coating film was examined. -Bending resistance The coated plate was bent to check the state of cracks in the coating film. The scratch-resistant coating film was strongly scratched twice with a nail to check the state of the coating film.

[0063]

[Table 7] Table 7 One-coat paint test results

(Examples 7 to 12 and Comparative Examples 10 to 19) Tables 8 to 10
The inks were prepared with the compositions shown in Table 1 above, and the performance tests of the inks were performed. The results are shown in Tables 11 to 13.

[0065]

[Table 8] Table 8 Ink composition (weight ratio) Note) Carmine 6BN: Azo organic pigment (Toyo Ink Mfg. Co., Ltd.)

[0066]

[Table 9] Table 9 Ink composition (weight ratio)

[0067]

[Table 10] Table 10 Ink composition (weight ratio)

1) Preparation of Ink Except for the curing agent and catalyst of the above ink composition, a sand mill was used
After being ground for a time, the mixture was diluted with toluene to a viscosity of 25-30 seconds / 20 ° C. using a # 3 Zahn cup to prepare. For those requiring a curing agent and a catalyst, they were added immediately before coating. 2) Evaluation method ・Cellophane adhesive tape peel test The ink prepared by the above method was coated with a coating rod # 1.
4, untreated polypropylene film (hereinafter referred to as untreated PP), corona discharge treated polypropylene film (hereinafter treated
(Referred to as PP) and dried at room temperature for 24 hours, and then a cellophane adhesive tape is applied to the ink-coated surface,
The peeled state of the coated surface when peeled off at a stretch was examined.・Heat seal strength test Cellophane pressure-sensitive adhesive tape peel test is performed in the same way as untreated PP.
Coating the ink on the treated PP, dried for 24 hours at room temperature, superposing the ink coated surface, subjected to heat sealed bonding conditions of 2 seconds at 120 ° C. -1 kg / cm ^2, after 24 hours Tensilon 180 ° peel strength was measured by using the following method (tensile speed: 50 mm / mi
n).

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[Table 11] Table 11 Ink test results

[0070]

[Table 12] Table 12 Ink test results

[0071]

[Table 13] Table 13 Ink test results

[0072]

The comparative examples 1, 2, 4, 5, 7, 8, and 10 to 15 are coating resin compositions proposed by the present inventors in Japanese Patent Application No. 11-237417. Comparative Examples 3, 6, 9, 16 and 17 are coating resin compositions containing a mixture of a carboxyl group-containing chlorinated polyolefin of Preparation Examples 1 to 3 and a polyol resin as a main component, and a curing agent added thereto. is there.
In Comparative Examples 18 and 19, a resin comprising a mixture of a resin obtained by reacting a carboxyl group-containing chlorinated polyolefin with a polyester polyol and a radical polymerizable unsaturated material and a polyol resin was used as a main component, and a curing agent Is a coating resin composition. When these are compared with the curable coating resin compositions of the examples,
Comparative Examples 1 and 2 show almost the same results as the Examples in the primer performance, whereas Comparative Example 3 is inferior in adhesion, moisture resistance, hot water resistance and gasoline resistance. Regarding the properties of the base coat paint, Comparative Examples 4 and 5 show almost the same results as the examples, whereas Comparative Example 6 is inferior in adhesion, moisture resistance, hot water resistance and gasoline resistance. In the one-coat paint properties, the same tendency as in the case of the base coat paint is shown, but in the comparative example, the anti-bending property,
Poor scratch resistance. With respect to the physical properties of the ink, the examples show good adhesion to the PP film, while the comparative examples are not always sufficient. The above results show that the curable coating resin composition of the present invention is useful.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takayuki Hirose 2-8-1 Iidacho, Iwakuni-shi, Yamaguchi Nippon Paper Industries Inside the Chemical Development Laboratory (72) Inventor Takaaki Ueda 2-8 Iidacho, Iwakuni-shi, Yamaguchi -1 Nippon Paper Industries Co., Ltd. Chemical Development Laboratory (72) Inventor Keiji Urata 2-8-1 Iidacho, Iwakuni-shi, Yamaguchi Prefecture Nippon Paper Industries Co., Ltd. Chemical Development Laboratory F-term (reference) 4J002 CK011 CK031 CK041 EA026 EA036 FD030 GH00 HA03 4J038 BA052 BA082 CB081 CB141 CB171 CG142 CH122 DA142 DA162 DA172 DB002 DD002 DD101 DD122 DF002 DG101 DG111 DG131 DG161 DG191 DG271 DG281 DG291 DG301 GA03 GA06 KA03 NA01 NA12 PB05 PB07 PB09 PC08

Claims (7)

[Claims] 1. A carboxyl group-containing chlorinated polyolefin obtained by graft modification using one or more compounds selected from α, β-unsaturated carboxylic acids and / or acid anhydrides thereof. A curable coating comprising an esterification reaction product with a polyol resin and / or a resin comprising a mixture of the esterification reaction product and a polyol resin as a main component, and blending an isocyanate compound or an alkyl etherified amino resin as a curing agent with the resin. Resin composition. 2. The polyol resin is an acrylic polyol,
Polyester polyol, polyether polyol, epoxy polyol, cellulose acetate butyrate,
Claim 1 is nitrified cotton, alkyd resin or a modified product thereof.
The curable coating resin composition according to the above. 3. The curable coating resin composition according to claim 1, wherein the chlorine content of the carboxyl group-containing chlorinated polyolefin is 10 to 50% by weight. 4. The graft ratio of one or more compounds selected from α, β-unsaturated carboxylic acids and / or acid anhydrides of carboxyl group-containing chlorinated polyolefins is from 1 to 1.
4. The curable coating resin composition according to claim 1, which is 0% by weight. 5. The curable coating resin according to claim 1, wherein the weight ratio of the carboxyl group-containing chlorinated polyolefin to the polyol resin to be esterified is in the range of 99/1 to 50/50. Composition. 6. The weight ratio of the esterification reactant to the polyol resin to be mixed is in the range of 90/10 to 10/90.
6. The curable coating resin composition according to any one of items 5 to 5. 7. An isocyanate group when the curing agent is an isocyanate compound, and an alkoxy group when the curing agent is an alkyl etherified amino resin is 0.5 to 1.5 mol per 1 mol of a hydroxyl group contained in the curable coating resin composition. The curable coating resin composition according to any one of claims 1 to 6, wherein